Process of making combustible material



narrate stares HARRY S. MORE, OF BROOKLINE, AND GUSTAVUS J. ESSELEN, 1TB, MASSACHUSETTS, ASSIGNORS TO ARTHUR D. LITTLE, INQ,

PATENT @FFECCE.

OF CAMBRIDGE,

MASSACHUSETTS, A CORPORATION OF MASSACHUSETTS.

PROCESS OF MAKING COMBUSTIIBLE IVIATERIAL.

No Drawing.

T 0 all whom it may concern Be it known that we, HARRY S. Moan, a citizen of the United States, and a resident of Brookline, in the county of Norfolk and State of Massachusetts, and GUsrAvUs J. EssELnN, Jr., a citizen of the United States, and a resident of Swampscott, county of Essex, and State of Massachusetts, have invented a certain new and useful Process of Making Combustible Material, of which the following is a specification.

()ur invention relates to a combustible material composed mainly of alcohol, and particularly to such a material which may be made up into a solid mass which may beburned in the open, or in a suitable container. v

The objects of our invention are to produce such a permanent material which is inexpensive to manufacture, which will burn freely without liquefication, which will not sweat or exude liquid to an objectionable denon-luminous, according to such selection.

A further object of the invention is to provide a process or method of making a combustible material as above described, in which the loss of material by evaporation or otherwise will be negligible, which is not limited to the use of any particular grade of the solid material employed, and in which a portion, at least, of the material used in the process and which may be undesirable or objectionable in the combustible material of the invention may be removed and conserved.

These and further objects will more fully appear in the following specification and claims.

In producing the product of the invention a suitable cellulose nitrate is dissolved in a volatile combustible solvent or solvent mixture. The solution is coagulated in a more or less comminuted or granular jellied con- Specification of Letters Patent.

ratemearvia is, tees.

Application filed September 10', 1919. Serial No. 322,954.

dition, as distinguished from a single 00- herent mass, by means of an excess of a nonsolvent liquid. The excess liquid is removed from the comminuted granules, which are then ready for the next step in the process.

A second solution of cellulose nitrate is prepared, to which is added a liquid nonsolvent, in quantity suflicient to bring the solution almost, but not quite, to the point of coagulation. Into this second solution the jelly granules, or lumps, are introduced, and if the proportions of granules and the second solution are properly regulated the mixture will set to a solid mass without appreciable exudation of liquid.

The last mentioned step of the process may be carried out in the container in which the material, is to be marketed and burned, or said final mixture may be made in any suitable vessel and the product out or otherwise shaped to any form desired.

The cause of the setting, when the granules are mixed with) the solution of the second step of the process, is believed to be due to diffusion of the non-solvent from the jelly granules or lumps into the .solution of the second step to a degree which causes coagulation of the solution, and binding of the entire mixture into a solid mass.

The product made by the proce% herein described is a permanent jell having a minimum tendency to exude liquid on standin The tendency of vthe jellied granules is toward expansion, which is mixed with the granules is toward contraction, but as the proportion of granules is largely in excess of that of the solution, the expansive effect exceeds the contractive effect, and the tendency of the solidified product as a whole is therefore toward expansion, and there will be no exudation of liquid.

As an illustration of one method of carrying out the process, approximately 5 grams of cellulose nitrate are dissolved in about 20 cc. of ethyl acetate and 70 cc. of denatured alcohol. 80 cc. of denatured alcohol with vigorous agitation, whereby the solution is coagulated in. the form of gelatinous lumps or granules suspended in a relatively large amount of liquid. The granules are allowed to soak in this liquid to permit a part, at least, of the solvent to difluse from the granor swararsoo'rrf the tendency of the solution This solution is mixed with ules into the liquid, to addv to the firmness of the granules. This soaking may take from 'ployed no coagulation will take place and the mixture will be fluid.

The second mixture is added to the gran ules produced in the first stage, in amount sufiiclent 'to cover the granules, and allowed to stand until the entire .mass solidifies. The

product-may now be packed and is ready for use. I

All'-of the steps of the process may be carried out at room temperature.

The general operation of the process, and

a concrete example thereof, have been described, but it is to be understood that the.

invention is not limited to the specific ingredients and the exact proportions given. Any solvent or mixture of solvents of suit able combustibility may be employedhrthe preparation of the granules or lumps, or in the liquid or liquids of the second step of the process. The solvents employed are solvents of cellulose nitrate of widely diflering grades, and the process and compound are not confined to the use of celluloseni trate of any articular degree of nitration.

The first mixture need not be made up in the form of lumps or granules. The nitrocellulose solution may be forced through small orifices into the nonsolvent, as in the 'manufacture of artificial silk, .thereby f orming the gelatinous granules in filamentary form, and the filamentous particles maybe formed into a solid mass as before.

The mixture of the gelatinous granules and the liquid of the second step may be made in the containers in which the product is to be'vended and burned; the mixture may be made in a separate vessel and-poured into the container before it jells; or the mixtures may be united in a large receptacle and, after solidificationof the final mixture, be cut or otherwise formedto any required --size and shape and packed as desired.

By proper selection of the combustible liqulds absorbed in the cellulose nitrate, the luminosity of the flame produced on combustion of the product may be modified. A-

'produc't, to be emplo ed for heating purposes only, may pro uce a non-luminous,

or feebly luminous flame. One burningwith a luminous flame, and .Which may be used for heating and illuminating purposes, may be produced.

For illuminating purposes the mixture may be made by the addition of from 10% .of 'odoriferous substances.

By the use of suitable proportions of denatured alcohol and methyl. or wood alcohol in the solutions and coagulating liquid,

:1 ,fuel which will burn with non-luminous flaniemayfl be produced.

As examples of solvents other than ethyl acetate, may. be mentioned ether-alcohol mixtures, methyl acetate, mixtures consisting chiefly of ethyl alcohol, acetone, other ketones, etc.

- By draining the excess liquid from the granules and successively supplying fresh quantities of non-solvent, the percentage of solvent in the granules will be gradually reduced and may be recovered from the drained ofi' liquid by known means.

For commercial and manufacturing reasons the preferred cellulose nitratefor use in the process is that usually referred to as pyroxylin. This material, has a nitrogen'content between 10.5% and 12.6%. It is completely soluble in butyl acetate with a viscosity of -50. In measuring the viscosity, a 5% solution of the pyroxylin in butyl acetate is used in an Ostwald viscometer at a temperature of 25. C., the viscosit of g ycerine taken at 100.

The above pyroxylin is given as an example only, and applicants desire to have 'it understood that any other cellulose nitrates having a nitrogen" content which is soluble in the solvents indicated, may be employed in the process.

In accordance with the provisions of the patent statutes the principle of the invention embodiment described is merely illustrative and thatthe invention may be carried out in other ways. v

Having now described the invention what is claimed and desired to be secured by Let- I ters Patent, is

1. The process of making an infusible solidified combustible material, which com= prises dissolving in. a volatile combustible compound the formula of which contains a carbonyl group, a cellulose nitrate having a nitrogen content which renders it soluble in the compound, coagulating the solution in an excess of a volatile combustible non-solvent,

and removing the excess of the non-solvent. 2. The process of making an 'infusible being expressed in relation to that v misses 1 solidified liquid combustible material, which comprises dissolving pyroxylin in a volatile combustible solvent the formula of which contains a carbonyl group, coagulating the solution in a volatile combustible non-solvent; preparing a second solution or pyroxylin in a suitable solvent, said second solution being close to the point of coagulation; and mixing the coagulated solution with the non-coagulated solution to solidify the mixture.

3. The process of making an infusible solidified liquid combustible material, which comprises (liSSOlVlIlg pyroxylin in a volatile combustible solvent the formula of which contains a carbonyl group, coagulating the solution in an excess of a volatile combustible non-solvent, removing the excess of non-solvent, preparing a second solution of pyroxylin close to the point of coagulation in a suitable solvent, and mixing the coagulated solution with the non-coagulated solution to solidfy the mixture.

l. The process or making an infusible solidified liquid combustible material, which comprises dissolving pyroxylin in a combustible solvent the formula of which contains a carbonyl group, and coagulating the solution into disjoined masses by the means of an excess of a volatile combustible non-solvent, and removing the excess.

5. The process of making an infusible solidified liquid combustible material, which comprises dissolving pyroxylin in a volatile combustible solventvthe formula of which contains a carbonyl group and alcohol, coagulating the solution'into disjoined masses by means of an excess of alcohol, and removing the excess of the alcohol.

6. The process of making an lnfusible solidified liquid combustible material, which comprises dissolving pyroxylin in ethyl acetate, adding a non-solvent in quantity suflicient to coagulate the solution in the form of disjoined masses, preparing a second solution by 1 dissolving pyroxylin close to the point of coagulation in ethyl acetate. and mixing the disjoined masses with the second solution to solidify the mixture.

7. The process of making an infusible sOlhllfitd liquid combustible material, which comprises dissolving pyroxylin in ethyl acetate, adding alcohol in quantity sufiicient to coagulate the solution in the form of disjoined masses, preparing a second solution by dissolving pyroxylin close to the point of coagulation in ethyl acetate and alcohol, and mixing the disjoined masses with the second solution to solidify the mixture.

8. The process of making an infusible solidified liquid combustible material, which comprises dissolving pyroxylin in ethyl acetate, adding an excess of alcohol in quan-' tity sufficient to coagulate the solution in the form of disjoined masses, removing the excess, preparing a second solution by dissolving pyroxylinclose to the point of coagulation in ethyl acetate and alcohol, and mixing the disjoined masses with the second solution to solidify the mixture.

9. The I process of making an intusible solidified liquid combustible material, which comprises dissolving 5 grams of cellulose nitra te in approximately 20 cc. of ethyl acetate and cc. of denatured alcohol, adding to approximately cc. of denatured alcohol with vigorous agitation, whereby the mixture is coagulated in the form of disjoined masses in an excess of liquid, allowing the masses to soak in the liquid; making a coagulating solution by dissolving 1.5 grams of cellulose nitrate in approximately (5.5 cc. of ethyl acetate and approximately 6.5 cc. of denatured alcohol, adding to the said coagulating solution approximately 32 cc. of denatured alcohol with agitation, andinixing the coagulating solution with the disjoined masses, whereby a solid mixture is produced.

10. The process of making an intusible solidified liquid combustible material, which comprises dissolving 5 grams of pyroxylin in approximately 20 cc. of ethyl acetate and 70 cc. of denatured alcohol, adding approximately 80 cc. of denatured alcohol with vigorous agitation, whereby the mixture is coagulated in the form of disjoined masses in an excess of liquid, allowing the masses to soak in the liquid; making a coagulating solution by dissolving 1.5 grams of pyroxylin in approximately 6.5 cc. of ethyl acetate and approximately 6.5 cc. of denatured alcohol, adding to the said coagulating solution approximately 32 cc. of denatured alcohol with agitation, adding a hydrocarbon distillate, and-mixing the coagulating solution with the disjoined masses, whereby a solid mixture is produced.

This specification signed and witnessed this 20th day of. August, 1919.

HARRY S. MORK. GUSTAVUS J. ESSELEN, JR.

\Vitnesses to the signature of Harry 5:3 Mork:

LAWRENCE HEMENWAY, CARL C. SORENSEN. Witnesses to the signature of Gustavus J "Esselen, J11:

EARL P. STEvnNsoN, CLARENCE J. Wear. 

